Cure controlled catalyzed mixtures of epoxy resins and curing agents containing mesogenic moieties, B-staged and cured products therefrom

ABSTRACT

Laminates containing one or more plies of substrate material impregnated with a composition containing (A) one or more epoxy resins, (B) one or more curing agent and (C) about 0.00005 to about 0.1 mole per epoxide equivalent of cure controlling catalyst, wherein at least one of components (A) or (B) contain at least one mesogenic moiety, which, optionally, has been subjected to either (a) the application of an electric field, (b) the application of a magnetic field, (c) drawing or shear forces, or (d) any combination thereof, are prepared.

FIELD OF THE INVENTION

The present invention concerns curable (thermosettable) mixtures of atleast one epoxy resin and at least one curing agent therefor, one ormore of which contain mesogenic moieties, and at least one curecontrolling catalyst therefor, as well as the cured (thermoset)compositions prepared therefrom.

BACKGROUND OF THE INVENTION

Epoxy resins are well established as a class of curable compositionswhich find efficacy in a myriad of applications. The curing of epoxyresins is effected by a wide range of curing agents including, forexample, the primary and secondary aliphatic, cycloaliphatic andaromatic polyamines; dicarboxylic acids and the anhydrides thereof;aromatic hydroxyl containing compounds; imidazoles; guanidines;urea-aldehyde resins and alkoxylated derivatives thereof;melamine-aldehyde resins and alkoxylated derivatives thereof;amidoamines; epoxy resin adducts; and various combinations thereof. Inaddition to said curing agents, one or more catalysts, such as aquaternary ammonium or phosphonium salts are frequently added toaccelerate the cure rate as well as to insure completeness of the cure.In the curing of epoxy resins with curing agents using catalysts, anumber of factors are critical to and interrelate to the curing processfor curable compositions containing mesogenic moieties relative toconventional, non-mesogenic curable compositions, directly as a resultof the presence of the mesogenic moieties. These factors include therelatively higher processing temperatures required to melt or dissolvemost mesogenic epoxy resins or mesogenic curing agents in the presenceof a catalyst as well as the development and maintainance of the desiredmorphology under the curing time and temperature profile employed. Thus,attempting to cure a curable mixture of epoxy resin and a curing agent,one or both of which contain mesogenic moieties, in the presence of acatalyst under conditions required for melt processing of said curablemixture frequently results in premature crosslinking of the matrix dueto the cure accelerating effect of the catalyst. The result of thispremature crosslinking is higher viscosities, lack of control over thetype of morphology attained in the cured state, underdevelopment of theliquid crystalline morphology and a subsequent deleterious impact onmechanical properties of the cured product.

The present invention provides novel curable mixtures comprising atleast one epoxy resin and at least one curing agent therefor, and atleast one cure controlling catalyst therefor; wherein, at least one ofthe epoxy resins or at least one of the curing agents contains at leastone mesogenic moiety.

It has been discovered that in curable compositions containing mesogenicmoieties, the use of a cure controlling catalyst allows higherprocessing temperatures to be used for melting or dissolving themesogenic epoxy resin and/or mesogenic curing agent, and lowerviscosities and greater control over the morphologies and properties arealso obtained. Thus, for curable compositions containing mesogenicmoieties of the present invention, lower levels of crosslinking at hightemperatures prior to catalyst activation and improved processabilityhave been achieved through the use of a cure controlling catalyst.Additionally, the fracture toughness achieved for curable compositionscontaining mesogenic moieties and a cure controlling catalyst has beenfound to be unexpectably higher than that obtained for curablecompositions which contain non-mesogenic moieties.

SUMMARY OF THE INVENTION

One aspect of the present invention pertains to curable compositionscomprising

(A) at least one epoxy resin having an average of more than one vicinalepoxide group per molecule;

(B) at least one curing agent for said epoxy resin; and

(C) at least one cure controlling catalyst;

wherein at least one of components (A) or (B) contain at least onemesogenic moiety.

A further aspect of the present invention pertains to the productresulting from B-staging (partially curing) said curable compositions.

A further aspect of the present invention pertains to the productresulting from curing said curable compositions wherein said curablecompositions have been subjected to either (a) the application of anelectric field, (b) the application of a magnetic field, (c) drawing orshear forces, or (d) any combination thereof either (i) before curing orprocessing, (ii) during curing or processing, or (c) both before andduring curing or processing.

A still further aspect of the present invention pertains to curedproducts such as, for example, coatings, laminates, composites,adhesives, castings, encapsulated articles, molded articles and the likeresulting from curing the aforementioned curable compositions.

The compositions and products of the present invention can consist of,consist essentially of or comprise the enumerated components.

The invention disclosed herein suitably can also be practiced in theabsence of any component which is not specifically disclosed orenumerated herein.

DETAILED DESCRIPTION OF THE INVENTION

DEFINITIONS

The term "cure controlling" means that the curable blend of epoxy resin,curing agent and cure controlling catalyst has a viscosity after 15minutes at 120° C. of 75 percent or less than the viscosity of a likecurable composition except that the catalyst is non-cure controlling.

The term "hydrocarbyl" as employed herein means any monovalent orpolyvlent aliphatic, cycloaliphatic, aromatic, aryl substitutedaliphatic or cycloaliphatic or aliphatic or cycloaliphatic substitutedaromatic groups. The aliphatic or cycloaliphatic groups can be saturatedor unsaturated. The "hydrocarbyl" groups can be monovalent or polyvalentas appropriate. Likewise, the term "hydrocarbyloxy" means a hydrocarbylgroup having an oxygen linkage between it and the carbon atom to whichit is attached.

The term "inertly substituted" means that the hydrocarbyl orhydrocarbyloxy group contains a substitutent that does not react withany of the components with which the compound containing suchsubstituents is associated. Such inert substituents include --CH₃,--OCH₃, --F, --Cl, --Br, --NO₂, --CN and the like.

The term "mesogenic" or "mesogen" as is used herein designates compoundscontaining one or more rigid rodlike structural units which have beenfound to favor the formation of liquid crystal phases in the case of lowmolar mass substances. Thus the mesogen or mesogenic moiety is thatstructure responsible for molecular ordering. The term mesogenic isfurther defined by R. A. Weiss (ed.) and C. K. Ober (ed.) inLiquid-Crystalline Polymers, ACS Symposium Series 435 (1989) on pages1-2: "The rigid unit responsible for the liquid crystalline behavior isreferred to as the mesogen," and "Liquid crystalline order is aconsequence solely of molecular shape anisotropy, such as found in rigidrodshaped molecules . . . " and "Liquid crystal is a term that is nowcommonly used to describe materials that exhibit partially ordered fluidphases that are intermediate between the three dimensionally orderedcrystalline state and the disordered or isotropic fluid state. Phaseswith positional and/or orientational long-range order in one or twodimensions are termed mesophases. As a consequence of the molecularorder, liquid crystal phases are anisotropic, i.e., their properties area function of direction." Further definition of the term mesogenic maybe found in Polymeric Liquid Crystals, Alexandre Blumstein (ed.), (1983)on pages 2-3: "Compounds forming small molecule thermotropic liquidcrystals usually have the following molecular structural features:--highlength:breadth (axial) ratio--rigid units such as 1,4-phenylene,1,4-bicyclooctyl, 1,4-cyclohexyl, etc., rigid central linkages betweenrings such as --COO--, --CH═CH--, --N═NO--, --N═N--, etc. --anisotropicmolecular polarization."

The terms "curable" and "thermosettable" are used synonymouslythroughout and mean that the composition is capable of being subjectedto conditions which will render the composition to a cured or thermosetstate or condition.

The terms "cured" and "thermoset" are used synonymously throughout. Theterm "thermoset" is defined by L. R. Whittington in Whittington'sDictionary of Plastics (1968) on page 239: "Resin or plastics compoundswhich in their final state as finished articles are substantiallyinfusible and insoluble. Thermosetting resins are often liquid at somestage in their manufacture or processing, which are cured by heat,catalysis, or some other chemical means. After being fully cured,thermosets cannot be resoftened by heat. Some plastics which arenormally thermoplastic can be made thermosetting by means ofcrosslinking with other materials." Resins which have been "cured" or"thermoset" are usually insoluble, infusible products.

The term "B-staging" or "B-staged" as employed herein designates thatpartial curing (partial thermosetting or partial crosslinking) of acurable composition has occurred. The term "B-stage" is defined in TheEpoxy Resin Formulators Training Manual, by The Society of the PlasticsIndustry, Inc. (1985) on pages 270-271 as:

"An intermediate stage in the reaction of certain thermosetting resinsin which the material softens when heated and swells when in contactwith certain liquids, but may not entirely fuse or dissolve."

The term "weak-nucleophilic" as employed herein means that a materialhas a nucleophilicity value "n" from greater than zero to less than 2.5,preferably from about 0.5 to about 2, more preferably from 1 to about 2,as described by C. G. Swain and C. B. Scott in J. Am. Chem. Soc., 75,141 (1953), which is incorporated herein by reference in its entirety.

NUMERICAL VALUES RECITED HEREIN

Any numerical values recited herein include all values from the lowervalue to the upper value in increments of one unit provided that thereis a separation of at least 2 units between any lower value and anyhigher value. As an example, if it is stated that the amount of acomponent is, for example, from 1 to 90, preferably 20 to 80, morepreferably from 30 to 70, it is intended that values such as 15-85,22-68, 43-51, 30-32 etc. are expressly enumerated in this specification.Usually, for values which are less than one, one unit is considered tobe 0.1; therefore, the minimum separation between any lower value andany higher value is 0.2. However, for the amounts of cure controllingcatalysts, one unit is considered to be 0.00001, 0.0001, 0.001, 0.01 or0.1 as appropriate. These are only examples of what is specificallyintended and all possible combinations of numerical values betwen thelowest value and the highest value enumerated are to be considered to beexpressly stated in this application in a similar manner.

CURE controlling CATALYSTS

Suitable cure controlling catalysts for effecting the reaction betweenthe epoxy resin and the curing agent include those disclosed in U.S.Pat. Nos. 4,594,291; 4,725,652; 4,925,901; 4,946,817; 5,134,239;5,140,079, and 5,169,473, all of which are incorporated reference. Ofthese cure controlling catalysts particularly suitable are thoseprepared by reacting an onium or amine compound with an acid having aweak-nucleophilic anion.

Some of the suitable cure controlling catalysts include thoserepresented by any of the following three formulas ##STR1## wherein eachL is independently a hydrocarbyl group or inertly substitutedhydrocarbyl group having from 1 to about 18, preferably from 1 to about12, more preferably from 1 to about 9, carbon atoms, which group alsocan contain one or more oxygen, sulfur or nitrogen atoms or two of suchL groups can combine to form a heterocyclic ring containing one or moreatoms other than carbon atoms; each L¹ is independently hydrogen or L; Zis nitrogen, phosphorus, sulfur or arsenic; W is a weak nucleophilicanion, preferably BF₄ ⁻, BCl₄ ⁻, NO₃ ⁻, F⁻, Cl--CH₂ --CH₂ --CO₂ ⁻,HO--CH₂ --CH₂ --CO₂ ⁻, SbF₅ ⁻, SbCl₅ ⁻, AsF₄ ⁻, AsCl₄ ⁻, FP(O)₂ (OH)⁻,(F)₂ P(O)₂ ⁻, F₃ B(OH)⁻, F₂ B(OH)₂ ⁻, ClP(O)₂ (OH)⁻ , more preferablyBF₄ ⁻, BCl₄ ⁻, z has a value of zero or 1 depending on the valence of Z;and q has a value equal to the valence of the anion W.

Particularly preferred cure controlling catalysts include, for example,tetrabutylphosphonium tetrahaloborate, ethyl(tritolyl)phosphoniumtetrahaloborate, ethyl(tritolyl)ammonium tetrahaloborate,benzyltrimethylammonium tetrahaloborate, tetrabutylammoniumtetrahaloborate, triethylamine.tetrahaloboric acid complex,tributylamine-tetrahaloboric acid complex,N,N'-dimethyl-1,2-diaminoethane.tetrahaloboric acid complex, and anycombination thereof and the like.

When employed to form the compositions of the present invention the curecontrolling catalysts are present in quantities which provide from about0.00005 to about 0.1, preferably from about 0.00005 to about 0.05, mostpreferably from about 0.0001 to about 0.03 mole of catalyst per epoxideequivalent.

When the cure controlling catalysts are employed in quantities belowabout 0.00005 mole per epoxide equivalent, either no catalytic effect orminimal catalytic effect at cure temperatures result.

When the cure controlling catalysts are employed in quantities aboveabout 0.1 mole per epoxide equivalent, overcatalysis or undesirablyshortened induction times at cure temperatures result.

EPOXY RESINS

The epoxy resins which can be employed to prepare the curablecompositions of the present invention include essentially anyepoxy-containing compound which contains an average of more than onevicinal epoxide group per molecule. The epoxide groups can be attachedto any oxygen, sulfur or nitrogen atom or the single bonded oxygen atomattached to the carbon atom of a --CO--O-- group in which said oxygen,sulfur or nitrogen atom or the carbon atom of the --CO--O-- group isattached to an aliphatic, cycloaliphatic, polycycloaliphatic or aromatichydrocarbon group which hydrocarbon group can be substituted with anyinert substituent including, but not limited to, halogen atoms,preferably fluorine, bromine or chlorine, nitro groups, and the like orsuch groups can be attached to the terminal carbon atoms of a compoundcontaining an average of more than one --(O--CHR^(a) --CHR^(a))_(t)--group where each R^(a) is independently hydrogen or an alkyl orhaloalkyl group, containing from one to about 2 carbon atoms, with theproviso that only one R^(a) group can be a haloalkyl group, and t has avalue from one to about 100, preferably from one to about 20, morepreferably from one to about 10, most preferably from one to about 5.Preferably, the vicinal epoxide groups are glycidyl ether, glycidylamine or glycidyl ester groups.

Suitable such epoxy resins which can be used to prepare the curablecompositions of the present invention include, for example, the glycidylethers or glycidyl amines represented by any of the following generalFormulas I, II, III, IV, V, VI, VII, VIII, IX or X ##STR2## wherein eachR is independently hydrogen or a monovalent hydrocarbyl orhydrocarbyloxy group having from one to about 10, preferably one toabout 4, carbon atoms, a halogen atom, preferably chlorine, bromine orfluorine, a nitro group, a nitrile group or a --CO--R² group; R² ishydrogen or a monovalent hydrocarbyl group having from one to about 10,preferably one to about 2, carbon atoms; n has a value of zero or one;each A is independently a direct single bond, a divalent hydrocarbylgroup having from one to about 20, preferably from one to about 6,carbon atoms, --O--, --CO--, --SO--, --SO₂ --, --S--, --S--S--, --CR¹═CR¹ --, --C.tbd.C--, --N═N--, --CR¹ ═N--, --N═CR¹ --, --O--CO--,--CO--O--, --S--CO--, --CO--S--, --NR¹ --CO--, --CO--NR¹ --, --CR¹ ═N--N═CR¹ --, --CO--CR¹ ═CR¹ --, --CR¹ ═CR¹ --CO--, --CO--O--N═CR¹ --,--CR¹ ═N--O--OC--, --CO--NR¹ --NR¹ --OC--, --CR¹ ═CR¹ --O--OC--,--CO--O--CR¹ ═CR¹ --, --O--CO--CR¹ ═CR¹ --, --CR¹ ═CR¹ --CO--O--,--(CHR¹)_(n') --O--CO--CR¹ ═CR¹ --, --CR¹ ═CR¹ --CO--O--, --(CHR¹)_(n')--, --(CHR¹)_(n') --CO--O--CR¹ ═CR¹ --, --CR¹ ═CR¹ --O--CO--(CHR¹)_(n')--, --CH₂ --CH₂ --CO--O--, --O--OC--CH₂ --CH₂ --, --C.tbd.C--C.tbd.C--,--CR¹ ═CR¹ --CR¹ ═CR¹ --, --CR¹ ═ CR¹ --C.tbd.C--, --C.tbd.C--CR¹ ═CR¹--, --CR¹ ═CR¹ --CH₂ --O--OC--, --CO--O--CH₂ --CR¹ ═CR¹ --,--O--CO--C.tbd.C--CO--O--, --O--CO--CR¹ ═CR¹ --CO--O--, --O--CO--CH₂--CH₂ --CO--O--, --S--CO--CR¹ ═CR¹ --CO--S--, --CO--CH₂ --NH--CO--,--CO--NH--CH₂ --CO--, --NH--C(--CH₃)═CH--CO--, --CO--CH═C(--CH₃)--NH--,--CR¹ ═C(--Cl)--, --C(--Cl)═CR¹ --, --CR¹ ═C(--CN)--, --C(--CN)═CR¹ --,--N═C(--CN)--, --C(--CN)═N--, --CR¹ ═C(--CN)--CO--O--,--O--CO--C(--CN)═CR¹ --, ##STR3## each A' is independently a divalenthydrocarbyl group having from one to about 10, preferably from one toabout 4, carbon atoms; A" is a divalent hydrocarbyl group having fromone to about 6, preferably from one to about 2, carbon atoms; each A¹ isindependently a --CO--, --O--CO--, --CO--O--, --CO--S--, --S--CO--,--CO--NR¹ -- or --NR¹ --CO--; each R¹ is independently hydrogen or amonovalent hydrocarbyl group having from one to about 6 carbon atoms,and is preferably hydrogen or a hydrocarbyl group containing one carbonatom; each R⁴ is independently hydrogen or a monovalent hydrocarbylgroup having from one to about 3 carbon atoms; each R⁵ is independentlyhydrogen, a monovalent hydrocarbyl group having from one to about 10,preferably from one to about 3, carbon atoms or a halogen atom,preferably chlorine or bromine; each R⁶ is independently hydrogen or amonovalent hydrocarbyl or halohydrocarbyl group having from one to about6, preferably one to about 2 carbon atoms; each R⁷ is independently amonovalent hydrocarbyl group having from one to about 6, preferably fromone to about 2 carbon atoms; Q is a direct bond, --CH₂ --S--CH₂ --,--(CH₂)_(n") --, or ##STR4## m has a value from about 0.001 to about 6,preferably from about 0.01 to about 3; m' has a value from one to about10, preferably from one to about 4; n' has a value of one or two, n" hasan average value of from about one to about 10; p has a value from zeroto about 30, preferably from zero to about 5 and p¹ has a value of fromone to about 30, preferably from one to about 3. The aromatic rings inFormulas I, II, III, IV, V, VI, VIII, IX and X can also contain one ormore heteroatoms selected from N, O, and S. The term "hydrocarbyl", whenapplied to the A" group of Formula VI, can also include one or moreheteroatoms selected from N, O, and S. Thus, A" can be, for example, the--CO-- or --CH₂ --O--CH₂ -- group.

Mesogenic epoxy resins include those represented by Formulas II, V, VIand IX wherein each A is independently selected from the aforementionedlisting, but with the proviso that the A group is other than: a singlebond, a divalent hydrocarbyl group having from one to 20 carbon atoms,--O--, --CO--, --SO--, --SO₂ --, --S-- or --S--S--; and with the provisothat at least 80 percent of the molecules making up the epoxy resin arepara substituted with respect to the bridging groups (-A-) in FormulasII, V, IX and by the direct bond in Formula VI, the substituentcontaining the glycidyl group(s), ##STR5## and the substituentcontaining the secondary hydroxyalkylidene group(s), --CH₂--C(OH)(R⁴)--CH₂ --, which are present when p or p¹ has a value greaterthan zero.

Representative epoxy resins which are substantially free of rodlikemesogenic moieties include, for example, the diglycidyl ethers of:resorcinol, hydroquinone, 4,4'-isopropylidenediphenol (bisphenol A),4,4'-dihydroxydiphenylmethane, 4,4'-dihydroxybenzophenone,3,3'5,5'-tetrabromo-4,4'-isopropylidenediphenol, 4,4'-thiodiphenol,4,4'-sulfonyldiphenol, 4,4'-dihydroxydiphenyl oxide,1,1-bis(4-hydroxyphenyl)-1-phenylethane,3,3',5,5'-tetrachloro-4,4'-isopropylidenediphenol A,3,3'-dimethoxy-4,4'-isopropylidenediphenol, dipropylene glycol,poly(propylene glycol), thiodiglycol; the triglycidyl ether oftris(hydroxyphenyl)methane; the polyglycidyl ethers of a phenol or alkylor halogen substituted phenol-aldehyde acid catalyzed condensationproduct (novolac resins); the tetraglycidyl amines of:4,4'-diaminodiphenylmethane or 4, 4' diaminodiphenylsulfone; thepolyglycidyl ether of the condensation product of a dicyclopentadiene oran oligomer thereof and a phenol or alkyl or halogen substituted phenol;the advancement reaction products of the aforesaid di and polyglycidylethers with aromatic di and polyhydroxyl or carboxylic acid containingcompounds including, for example hydroquinone, resorcinol, catechol,2,4-dimethylresorcinol, 4-chlororesorcinol, tetramethylhydroquinone,4,4'-isopropylidenediphenol (bisphenol A),4,4'-dihydroxydiphenylmethane, 4,4'-thiodiphenol, 4,4'-sulfonyldiphenol,2,2' -sulfonyldiphenol, 4,4'-dihydroxydiphenyl oxide,4,4'-dihydroxybenzophenone, 1,1-bis(4-hydroxyphenyl)-1-phenylethane,4,4'-bis(4(4-hydroxyphenoxy)phenylsulfone)diphenyl ether,4,4'-dihydroxydiphenyl disulfide,3,3',3,5'-tetrachloro-4,4'-isopropylidenediphenol,3,3',3,5'-tetrabromo-4,4'-isopropylidenediphenol,3,3'-dimethoxy-4,4'-isopropylidenediphenol;1,1'-bis(4-hydroxyphenyl)cyclohexane, phloroglucinol, pyrogallol,2,2',5,5'-tetrahydroxydiphenyl sulfone, tris(hydroxyphenyl)methane,dicyclopentadiene diphenol, tricyclopentadiene diphenol, terephthalicacid, isophthalic acid, adipic acid; or any combination of theaforementioned epoxy resins and the like.

Representative epoxy resins which contain rodlike mesogenic moietiesinclude, for example, the diglycidyl ethers of:4,4'-dihydroxy-alpha-methylstilbene, 4,4'-dihydroxybenzanilide,4,4'-dihydroxyazoxybenzene, 4,4'-dihydroxybiphenyl,4,4'-dihydroxydiphenylazomethine, 4,4'-dihydroxydiphenylacetylene,4,4'-dihydroxystilbene, 4,4'-dihydroxy-alpha-cyanostilbene,4,4'-dihydroxyazobenzene, 4,4'-dihydroxyazoxybenzene,4,4'-dihydroxychalcone, 4-hydroxyphenyl-4-hydroxybenzoate; thetetraglycidyl amines of: 4,4'-diaminostilbene,N,N'-dimethyl-4,4'-diaminostilbene, 4,4'-diaminobenzanilide,4,4'-diaminobiphenyl, 4,4'-diamino-alpha-methylstilbene; the advancementreaction products of the aforesaid di and polyglycidyl ethers witharomatic di and polyhydroxyl or carboxylic acid containing compoundsincluding, for example 4,4'-dihydroxybiphenyl,4,4'-dihydroxy-alpha-methylstilbene, 4,4'-dihydroxybenzanilide,bis(4-hydroxyphenyl)terephthalate,N,N'-bis(4-hydroxyphenyl)terephthalamide,bis(4'-hydroxybiphenyl)terephthalate, 4,4'-dihydroxyphenylbenzoate,bis(4'-hydroxyphenyl)-1,4-benzenediimine; 4,4'-benzanilidedicarboxylicacid, 4,4'-phenylbenzoatedicarboxylic acid, 4,4'-stilbenedicarboxylicacid; or any combination of the aforementioned epoxy resins and thelike.

These epoxy resins can be prepared generally by reacting a compoundcontaining an average of more than one active hydrogen atom per moleculesuch as a compound containing an average of more than one primary orsecondary amine group, carboxyl group, aliphatic, cycloaliphatic oraromatic hydroxyl group with an epihalohydrin in the presence of asuitable catalyst and in the presence or absence of a suitable solventat a temperature suitably from about 0° C. to about 100° C., moresuitably from about 20° C. to about 80° C., most suitably from about 20°C. to about 65° C.; at pressures suitably from about 30 mm Hg vacuum toabout 100 psia., more suitably from about 30 Hg vacuum to about 50psia., most suitably from about 60 mm Hg vacuum to about atmosphericpressure; for a time sufficient to complete the reaction, usually fromabout 0.5 to about 24, more usually from about 1 to about 12, mostusually from about 1 to about 8 hours; and using from about 1.5:1 to100:1, preferably from about 2:1 to about 50:1, most preferably fromabout 3:1 to about 20:1 moles of epihalohydrin per hydroxyl group. Thisinitial reaction, unless the catalyst is an alkali metal or alkalineearth metal hydroxide employed in stoichiometric quantities, produces ahalohydrin intermediate which is then reacted with a basic actingsubstance to convert the vicinal halohydrin groups to epoxide groups.The resultant product is a glycidyl compound. When the active hydrogencompound contains a hydroxyl group, the resultant product is a glycidylether; when the active hydrogen compound contains an amine group, theresultant product is a glycidyl amine; and when the active hydrogencompound contains a carboxyl group, the resultant product is a glycidylester.

Advancement reaction of di- and polyglycidyl compounds can be performedby known methods which usually includes combining one or more suitablecompounds having an average of more than one active hydrogen atom permolecule, including, for example, dihydroxy aromatic, dithiol ordicarboxylic acid compounds or compounds containing one primary amine oramide group or two secondary amine groups and the di- or polyglycidylcompunds in the presence or absence of a suitable solvent with theapplication of heat and mixing to effect the advancement reaction. Theepoxy resin and the compound having more than one active hydrogen atomper molecule are reacted in amounts which provide suitably from about0.01:1 to about 0.95:1, more suitably from about 0.05:1 to about 0.8:1,most suitably from about 0.10:1 to about 0.5:1 active hydrogen atoms perepoxy group. The advancement reaction can be conducted at atmospheric,superatmospheric or subatmospheric pressures at temperatures of fromabout 20° C. to about 260° C., more suitably from about 80° C. to about240° C., most suitably from about 100° C. to about 200° C. The timerequired to complete the advancement reaction depends upon thetemperature employed. Higher temperatures require shorter periods oftime whereas lower temperatures require longer periods of time.Generally, times of from about 5 minutes to about 24 hours, moresuitably from about 30 minutes to about 8 hours, most suitably fromabout 30 minutes to about 4 hours are employed. A catalyst, including,for example, phosphines, quaternary ammonium compounds, phosphoniumcompounds and tertiary amines, is frequently added to facilitate theadvancement reaction and is usually employed in quantities of from about0.01 to about 3, preferably from about 0.03 to about 1.5, mostpreferably from about 0.05 to about 1.5 percent by weight based upon theweight of the epoxy resin.

Also suitable as the epoxy resins are the compounds containing athiirane, ##STR6## group which correspond to those compounds containingthe glycidyl, ##STR7## group. CURABLE COMPOSITIONS

The curable compositions of the present invention are prepared by mixingtogether one or more epoxy resins and one or more curing agents forepoxy resins, one or both of which contain mesogenic moieties, and oneor more cure controlling catalysts. For epoxy resins and/or curingagents which are solids, frequently, it is convenient to first melt theepoxy resin, then dissolve the curing agent therein followed by additionof the cure controlling catalyst. It is also operable to melt the curingagent then dissolve the epoxy resin therein followed by addition of thecure controlling catalyst, although this is generally less preferred.

The curing agents are employed in amounts which will effectively curethe curable mixture, with the understanding that these amounts willdepend upon the particular curing agent and epoxy resin employed.Generally, suitable amounts are from about 0.80:1 to about 1.50:1,preferably from about 0.95:1 to about 1.05:1 equivalents of curing agentper equivalent of epoxide group in the epoxy resin at the conditionsemployed for curing.

The curing of the curable compositions of the present invention can beconducted at atmospheric, superatmospheric or subatmospheric pressuresat temperatures of from about 0° C. to about 300° C., preferably fromabout 50° C. to about 240° C., more preferably from about 150° C. toabout 220° C. The time required to complete curing depends upon thetemperature employed. Higher temperatures require shorter periods oftime whereas lower temperatures require longer periods of time.Generally, however, times of from about one minute to about 48 hours,preferably from about 15 minutes to about 8 hours, more preferably fromabout 30 minutes to about 3 hours are suitable.

CURING AGENTS

Suitable curing agents which can be used to prepare the curablecompositions of the present invention include, for example, aliphatic,cycloaliphatic, polycycloaliphatic or aromatic primary monoamines;aliphatic, cycloaliphatic, polycycloaliphatic or aromatic primary andsecondary polyamines; carboxylic acids and anhydrides thereof; aromatichydroxyl containing compounds; imidazoles; guanidines; urea-aldehyderesins; melamine-aldehyde resins; alkoxylated urea-aldehyde resins;alkoxylated melamine-aldehyde resins; amidoamines; epoxy resin adductsall, none, or a part of which :may contain one or more mesogenicmoieties; combinations thereof and the like. Particularly suitablecuring agents which do not include mesogenic moieties include, forexample, methylenedianiline, dicyandiamide, ethylene diamine,diethylenetriamine, triethylenetetramine, tetraethylenepentamine,urea-formaldehyde resins, melamine-formaldehyde resins, methylolatedurea-formaldehyde resins, methylolated melamine-formaldehyde resins,phenol-formaldehyde novolac resins, cresol-formaldehyde novolac resins,sulfanilamide, diaminodiphenylsulfone, diethyltoluenediamine,t-butyl-toluenediamine, bis-4-aminocyclohexylamine, isophoronediamine,diaminocyclohexane, hexamethylenediamine, piperazine,aminoethylpiperazine, 2,5-dimethyl-2,5-hexanediamine,1,12-dodecanediamine, tris-3-aminopropylamine, combinations thereof andthe like. Particularly suitable curing agents which contain mesogenicmoieties include, for example, 4,4'-diaminostilbene,4,4'-diamino-alpha-methylstilbene, 4,4'-diaminobenzanilide,4,4'-bis(amino-phenoxy)-alpha-methylstilbene,4,4'-dihydroxy-alpha-methylstilbene, 4,4'-dihydroxy-alpha-cyanostilbene,4,4'-dihydroxystilbene, 4,4'-dihydroxy-2,2'-dimethylazoxybenzene,4,4'-dihydroxy-α,α'-diethylstilbene, 4,4' -dihydroxybenzanilide,4,4"-dihydroxybiphenylbenzoate, bis(4-hydroxyphenyl)terephthalate,bis(N,N'-4-hydroxyphenyl)terephthalamide,bis(4'-dihydroxybiphenyl)terephthalate, 4,4'-dihydroxyphenylbenzoate,1,4-bis(4'-hydroxyphenyl-1'-carboxamide)benzene,1,4-bis(4'-hydroxyphenyl-1'-carboxy)benzene,4,4'-bis(4"-hydroxyphenyl-1"-carboxy)biphenyl,bis(4'-hydroxyphenyl)-1,4-benzenediimine, 4,4'-benzanilide dicarboxylicacid, 4,4'-phenylbenzoate dicarboxylic acid, 4,4'-stilbene dicarboxylicacid, or any combination thereof and the like.

AMOUNT OF COMPONENT(S) CONTAINING MESOGENIC MOIETIES

The amounts of mesogenic moiety required to improve one or moreproperties of the cured products resulting from the curable compositionsof the present invention vary substantially and depend upon theparticular chemical structure of the mesogenic moiety or moieties used,the aspect ratio of the mesogenic moiety or moieties used, the curetemperature(s) used, the cure time(s) used, and other such variables.Usually the amount of components containing a mesogenic moiety in thecurable compositions are preferably from about 5 percent to 100 percent,more preferably from about 10 percent to 100 percent, most preferablyfrom about 20 percent to 100 percent of the epoxy and/or thiirane resinsand components reactive with an epoxide or thiirane group employed inthe composition.

B-STAGING (PARTIAL CURING)

It is also operable to partially cure (B-stage) the curable compositionsof the present invention and then complete the curing at a later time.B-staging can be accomplished by heating at a temperature for such atime that only partial curing is produced. Usually, the curetemperatures are employed for B-staging, however, for a shorter periodof time. Generally, the extent of B-staging is monitored usinganalytical methods such as viscosity measurement, differential scanningcalorimetry for residual cure energy or infrared spectrophotometricanalysis for unreacted curable functional groups.

It is frequently of value to "B-stage" the curable compositions of thisinvention in order to chain extend the resin. This chain extension isrequired for some mesogen-containing curable compositions in order toachieve liquid crystal character. B-staging can also be employed toincrease the temperature range at which a particular curable compositionis liquid crystalline and to control the degree of crosslinking duringthe final curing stage.

ORIENTATION

As a result of the mesogenic moieties being present in one or more ofthe components of the curable compositions of the present invention,electric or magnetic fields, drawing and/or shear stresses can beapplied before and/or during processing and/or curing for the purpose oforienting the liquid crystal phase contained or developed therein. Theeffect of this orientation is an improvement in mechanical properties.As specific examples of these methods, Finkelmann, et al, Macromol.Chem., volume 180, pages 803-806 (March, 1979) induced orientation inthermotropic thermoplastic methacrylate copolymers containing mesogenicside chain groups decoupled from the main chain via flexible spacers inan electric field. Within the nematic liquid crystalline transitiontemperature range for one of the copolymers, homeotropic orientation wasachieved with a half-time of approximately 10 seconds at 8 volts d.c. Athigher voltages, turbulent flow disrupted the homeotropic orientation. Asecond copolymer within the nematic liquid crystalline transitiontemperature range gave reversible homeotropic orientation with anorientation time of less than 200 mseconds in a 50 Hz d.c. electricfield. Threshold voltage was approximately 6 volts and the relaxationhalf-time was approximately 5 seconds. Thus, for the orientation of thecurable blends of the present invention which contain or develop liquidcrystal moieties, it is frequently of value to conduct simplepreliminary experiments over the range of experimental conditions to beemployed, including voltage to be applied and time to be used forapplication of the voltage to a given mesophase at a given temperature.In this manner, an indication of the critical electric field strength,orientation time and relaxation time for the mesophase to be orientedcan be obtained and conditions not conducive to orientation, such asflow instability, can be avoided. Orientation of mesogenic side chaingroups decoupled from the thermoplastic polymer main chain via flexiblespacers in a magnetic field has been demonstrated by Roth and Kruecke,Macromol. Chem., volume 187, pages 2655-2662 (November, 1986). Withinthe broad temperature range of approximately -120° C. to 200° C.,orientation of the polymers was observed (anisotropy in the motionalprocesses as shown by change in line width of proton magnetic resonancesignals as a function of temperature). In order to achieve macroscopicorientation in a magnetic field of about 2 T it was found that thechoice of proper temperature is important such that the ordering effectof the magnetic field overcomes the disordering effect of thermal motionand that sufficient molecular mobility is present to allow for theordering to occur. Furthermore, this proper temperature was found tovary as a function of the particular mesogen-containing polymer to beoriented. Thus, for the orientation of the curable blends of the presentinvention which contain or develop liquid crystal moieties, it isfrequently of value to conduct simple preliminary experiments over therange of experimental conditions to be employed, including the magneticfield to be applied and time to be used for application of the magneticfield to a given mesophase at a given temperature. In this manner, anindication of the critical magnetic field strength, orientation time andrelaxation time for the mesophase to be oriented can be obtained andconditions not conducive to orientation, such as improper temperaturerange, can be avoided. Magnetic field induced orientation of mesogenicmain chain containing thermoplastic polymers has been demonstrated byMoore, et al, ACS Polymeric Materials Sciences and Engineering, volume52, pages 84-86 (April-May, 1985). At the melt temperature for theliquid crystalline thermoplastic copolymer of p-hydroxybenzoic acid(80%) and polyethylene terephthalate (20%) the threshold for orientationwas found to be approximately 0.4 T, with the degree of orientation(order parameter) depending on the strength of the magnetic field.Relaxation of the orientation once the polymer is removed from themagnetic field depends on the amount of time that the polymer spent inthe magnetic field. Thus, for the liquid crystalline thermoplasticpolymer maintained in a 6.3 T magnetic field, maximum relaxation timewas approximately 15 minutes, while the liquid crystalline thermoplasticpolymer maintained in a 2 T or less magnetic field exhibited a maximumrelaxation time of less than one minute. An equation delineating thebalance between the ordering effect of the magnetic field and thedisordering effect of thermal motion is given for domains of radius a asfollows:

    X.sub.a ·Ht.sup.2 ·a.sup.2 =kT/a

where Ht is the threshold magnetic field and X_(a) is the differencebetween the magnetic susceptibilities of the polymer when alignedparallel and perpendicular to the field.

Magnetic and electric field orientation of low molecular weightmesogenic compounds is discussed by W. R. Krigbaum in Polymer LiquidCrystals, pages 275-309 (1982) published by Academic Press, Inc.

In addition to orientation by electric or magnetic fields, polymericmesophases can be oriented by shear forces, for example, using hearrates as low as 0.1 sec⁻¹ to as high as 10,000 sec⁻¹, which are inducedby drawing and/or flow through dies, orifices and mold gates. A generaldiscussion for orientation of thermotropic liquid crystal polymers bythis method is given by S. K. Garg and S. Kenig in High ModulusPolymers, pages 71-103 (1988) published by Marcel Dekker, Inc. and S.Keneg, Polymer Engineering and Science, volume 29, number 16, pages1136-1141 (August, 1989). For the orientation by shear forces of thecurable blends of the present invention which contain or develop liquidcrystal moieties, it is frequently of value to conduct simplepreliminary experiments over the range of experimental conditions to beemployed, including total shear strain to be applied and time to be usedfor application of the shear force to a given mesophase at a giventemperature. In this manner, an indication of the critical total shearstrain, orientation time and relaxation time for the mesophase to beoriented can be obtained and conditions not conducive to orientation,such as tumbling of domain structure, can be avoided. For themesomorphic systems based on using latent catalysts, this shearorientation can be produced by processing methods such as injectionmolding, extrusion, pultrusion, filament winding, compression moldingfilming and prepreging. All of the aforementioned periodicals and booksare incorporated herein by reference in their entirety.

OTHER COMPONENTS

The curable compositions of the present invention can be blended withother materials such as solvents or diluents, fillers, pigments, dyes,flow modifiers, thickeners, reinforcing agents, mold release agents,wetting agents, stabilizers, fire retardant agents, surfactants or anycombination thereof and the like.

These additives are added in functionally equivalent amounts, e.g., thepigments and/or dyes are added in quantities which will provide thecomposition with the desired color; however, they are suitably employedin amounts of from about zero to about 20, more suitably from about 0.5to about 5, most suitably from about 0.5 to about 3 percent by weightbased upon the weight of the total blended compositions.

Solvents or diluents which can be employed herein include, for example,hydrocarbons, ketones, glycol ethers, aliphatic ethers, cyclic ethers,esters, amides, combinations thereof and the like. Particularly suitablesolvents or diluents include, for example, toluene, xylene,methylethylketone, methylisobutylketone, diethylene glycol methyl ether,dipropylene glycol methyl ether, dimethylformamide,N-methylpyrrolidinone, tetrahydrofuran, dioxane, propylene glycol methylether or any combination thereof and the like.

The modifiers such as thickeners, flow modifiers and the like can besuitably employed in amounts of from zero to about 10, more suitablyfrom about 0.5 to about 6, most suitably from about 0.5 to about 4percent by weight based upon the weight of the total composition.

Reinforcing materials which can be employed herein include natural andsynthetic fibers in the form of woven fabric, mats, monofilament,multifilament, unidirectional fibers, rovings, random fibers orfilaments, inorganic fillers or whiskers, hollow spheres, and the like.Suitable reinforcing materials include glass, ceramics, nylon, rayon,cotton, aramid, graphite, polyalkylene terephthalates, polyethylene,polypropylene, polyesters or any combination thereof and the like.

Suitable fillers which can be employed herein include, for example,inorganic oxides, ceramic microspheres, plastic microspheres, glassmicrospheres, inorganic whiskers, calcium carbonate or any combinationthereof and the like.

The fillers can be employed in amounts suitably from about zero to about95, more suitably from about 10 to about 80, most suitably from about 40to about 60 percent by weight based upon the weight of the totalcomposition.

UTILIZATION

The curable compositions of the present invention can be employed incoating, casting, encapsulation, electronic or structural laminate orcomposite, filament winding, molding, and the like applications.

The following examples are illustrative of the present invention, butare not to be construed as to limiting its scope in any manner.

COMPARATIVE EXPERIMENT A

Preparation of a Cured Epoxy Resin Containing Non-mesogenic Moieties(Not an Example of the Present Invention)

A. Preparation of B-Staged Resin

The following components are added to a 12 liter round bottom flask andheated to 150° C.:

1. Diglycidyl ether of bisphenol A--2863.41 grams (EEW=174.0; 16.456epoxide equiv.),

2. A 2.2 functional epoxy resin having a dicyclopentadienebackbone--3702.69 grams (EEW=225.0; 16.456 epoxide equivants),

3. A 3.6 functional phenol/formaldehyde novolac resin--1711.46 grams(--OH equiv. wt. =104.0; 16.456 phenolic equiv.),

4. Tetrabromobisphenol A--3580.91 grams (--OH equiv. wt. =272.0; 13.165phenolic equiv.).

At 150° C., 141.52 grams of sulfanilamide (amine hydrogen equiv. wt.=43.0525; 3.291 amine hydrogen equiv.) is added. After 30 minutes ofstirring, the resin is cooled to 100° C. and 62.07 milliliters (0.0717mole; 0.00178 mole of catalyst per epoxide group) of a 40 weight percentsolution of tetra-n-butylphosphonium fluoroborate (422.5 molecularweight) in methanol is added. The methanol is then removed from theresin by applying a vacuum to the round bottom flask and externallycollecting the vapors obtained. The resultant B-staged resin is thenpoured from the flask and allowed to cool to room temperature.

B. Curing of B-Staged Resin

For the preparation of a cured composition, 115 grams of the B-stagedresin prepared in A above is heated to 150° C. After heating to 150° C.,the resin is poured into a 7.5 inch×7.0 inch×0.125 inch (19.05 cm×17.78cm×0.3175 cm) glass mold preheated to 150° C. The cure schedule used forthe resin consists of 4 hours at 150° C., 1 hour at 175° C. and 2 hoursat 200° C. The casting obtained is then cooled to room temperature andremoved from the mold for evaluation. The resultant cured product hasthe properties reported in Table I.

EXAMPLE 1

Preparation of a Cured Epoxy Resin Composition Containing the DiglycidylEther of 4.4'-Dihydroxy-alpha-methylstilbene

A. Preparation of B-Staged Resin

The following components are combined and heated to 150° C. on a hotplate:

1. Diglycidyl ether of 4,4'-dihydroxy-alpha-methylstilbene--31.25grams--(EEW =176.6; 0.177 epoxide equiv.),

2. Diglycidyl ether of bisphenol A--15.40 grams (EEW =174.0; 0.088epoxide equiv.),

3. A 2.2 functional epoxy resin having a dicyclopentadienebackbone--19.91 grams (EEW =225; 0.088 epoxide equiv.),

4. A 3.6 functional phenol/formaldehyde novolac resin--18.41 grams (--OHequiv. wt. =104.0; 0.177 phenolic equiv.),

5. Tetrabromobisphenol A--38.51 grams (--OH equiv. wt. =272.0; 0.141phenolic equiv.),

6. Sulfanilamide--1.52 grams (amine hydrogen equiv. wt. =43.0525; 0.035amine hydrogen equiv.).

After heating to 150° C., the mixture is stirred until all thecomponents have either melted or dissolved. The resin is then cooled to140° C. and 0.67 milliliter (0.000774 mole; 0.00179 mole of catalyst perepoxide group) of a 40 weight percent solution oftetra-n-butylphosphonium fluoroborate (422.5 molecular weight) inmethanol is added. After additional stirring, the methanol is removedfrom the B-staged resin by applying a vacuum using a bell jar.

B. Curing of B-Staged Resin

After the methanol is removed, as evidenced by no observable outgassing,the B-staged resin prepared in A. above is poured into a 7.5 inch×7.0inch×0.125 inch (19.05 cm×17.78 cm×0.3175 cm) glass mold preheated to150° C. The cure schedule used for the resin consists of 4 hours at 150°C., 1 hour at 175° C. and 2 hours at 200° C. The casting obtained usingthis cure schedule is then cooled to room temperature and removed fromthe mold for evaluation. The resultant cured product has the propertiesreported in Table I.

EXAMPLE 2

Preparation of a Cured Epoxy Resin Composition Containing the DiglycidylEther of 4,4'-Dihydroxy-alpha-methylstilbene and 44'-Dihydroxy-alpha-methylstilbene

A. Preparation of B-Staged Resin

The following components are combined and heated to 150° C. on a hotplate:

1. Diglycidyl ether of 4,4'-dihydroxy-alpha-methylstilbene--34.35grams--(EEW =176.6; 0.195 epoxide equiv.),

2. Diglycidyl ether of bisphenol A--16.92 grams (EEW =174.0; 0.097epoxide equiv.),

3. A 2.2 functional epoxy resin having a dicyclopentadienebackbone--21.88 grams (EEW =225; 0.097 epoxide equiv.),

4. A 3.6 functional phenol/formaldehyde novolac resin--20.23 grams (--OHequiv. wt. =104.0; 0.194 phenolic equiv.),

5. Tetrabromobisphenol A--21.16 grams (--OH equiv. wt. =272.0; 0.078phenolic equiv.),

6. 4,4'-Dihydroxy-alpha-methylstilbene--8.79 grams (--OH equiv. wt.=113.145; 0.078 phenolic equiv.),

7. Sulfanilamide--1.67 grams (amine hydrogen equiv. wt. =43.0525; 0.039amine hydrogen equiv.).

After heating to 150° C., the mixture is stirred until all thecomponents have either melted or dissolved. The resin is then cooled to140° C. and 0.73 milliliters (0.000843 mole; 0.00178 mole of catalystper epoxide group) of a 40 weight percent solution oftetra-n-butylphosphonium fluoroborate (422.5) molecular weight inmethanol is added. After additional stirring, the methanol is removedfrom the B-staged resin by applying a vacuum using a bell jar.

B. Curing of B-Staged Resin

After the methanol is removed, as evidenced by no observable outgassing,the B-staged resin prepared in A. above is poured into a 7.5 inch×7.0inch×0.125 inch (19.05 cm×17.78 cm×0.3175 cm) glass mold preheated to150° C. The cure schedule used for the resin consists of 4 hours at 150°C., 1 hour at 175° C. and 2 hours at 200° C. The casting obtained usingthis cure schedule is then cooled to room temperature and removed fromthe mold for evaluation. The resultant cured product has the propertiesreported in Table I.

EXAMPLE 3

Preparation of a Cured Epoxy Resin Composition Containing the DiglycidylEther of 4,4'-Dihydroxy-alpha-methylstilbene and4,4'-Dihydroxy-alpha-methylstilbene

A. Preparation of B=Staged Resin

The following components are combined and heated to 160° C. in a forcedair convection oven:

1. Diglycidyl ether of 4,4'-dihydroxy-alpha-methylstilbene--66.89grams--(EEW=178.1; 0.375 epoxide equiv.),

2. A 3.6 functional phenol/formaldehyde novolac resin--19.50 grams (--OHequiv. wt. =104.0; 0.187 phenolic equiv.),

3. 4,4'-Dihydroxy-alpha-methylstilbene--16.99 grams (--OH equiv. wt.=113.145; 0.150 phenolic equiv.),

4. Sulfanilamide--1.62 grams (amine hydrogen equiv. wt. =43.0525; 0.038amine hydrogen equiv.).

After heating to 160° C., the mixture is stirred until all thecomponents have either melted or dissolved and 0.79 milliliters(0.000913 mole; 0.00199 mole of catalyst per epoxide group) of a 40weight percent solution of tetra-n-butylphosphonium fluoroborate (422.5molecular weight) in methanol is added. After additional stirring, themethanol is removed from the B-staged resin by applying a vacuum using abell jar.

B. curing of B-Staged Resin

After the methanol is removed, as evidenced by no observable outgassing,the B-staged resin prepared in A. above is poured into a 7.5 inch×7.0inch×0.125 inch (19.05 cm×17.78 cm×0.3175 cm) glass mold preheated to160° C., which is then cooled to 135° C. The cure schedule used for theresin consists of 3 hours at 135° C., 1 hour at 150° C., 1 hour at 175°C., and 2 hours at 200° C. The casting obtained using this cure scheduleis cooled to room temperature and removed from the mold for evaluation.The resultant cured product has the properties reported in Table I.

EXAMPLE 4

Preparation of a Cured Epoxy Resin Composition Containing the DiglycidylEther of 4,4'-Dihydroxy-alpha-methylstilbene and4,4'-Dihydroxy-alpha-methylstilbene

A. Preparation Of B-Staged Resin

The following components are combined and heated to 160° C. in a forcedair convection oven:

1. Diglycidyl ether of 4,4'-dihydroxy-alpha-methylstilbene--66.10grams--(EEW=178.1; 0.371 epoxide equiv.),

2. A 3.6 functional phenol/formaldehyde novolac resin--19.30 grams (--OHequiv. wt. =104.0; 0.185 phenolic equiv.),

3. 4,4'-Dihydroxy-alpha-methylstilbene--20.99 grams (--OH equiv. wt.=113.145; 0.185 phenolic equiv.).

After heating to 160° C., the mixture is stirred until all thecomponents have either melted or dissolved. The resin is then cooled to150° C. and 0.78 milliliters (0.000901 mole; 0.00199 mole of catalystper epoxide group) of a 40 weight percent solution oftetra-n-butylphosphonium fluoroborate (422.5 molecular weight) inmethanol is added. After additional stirring, the methanol is removedfrom the B-staged resin by applying a vacuum using a bell jar.

B. Curing of B-Staged Resin

After the methanol is removed, as evidenced by no observable outgassing,the B-staged resin prepared in A. above is poured into a 7.5 inch×7.0inch×0.125 inch (19.05 cm×17.78 cm×0.3175 cm) glass mold preheated to160° C., which is then cooled to 130° C. The cure schedule used for theresin consists of 3 hours at 130° C., 1 hour at 150° C., 1 hour at 175°C., and 4 hours at 200° C. The casting obtained using this cure scheduleis cooled to room temperature and removed from the mold for evaluation.The resultant cured product has the properties reported in Table I.

                                      TABLE I                                     __________________________________________________________________________    COMPONENTS   Comp.                                                            RESULTS      Expt A*                                                                            Ex. 1                                                                              Ex. 2                                                                              Ex. 3                                                                              Ex. 4                                        __________________________________________________________________________    Equivalents of phenolic                                                                    0.9  0.9  0.9  0.9  1.0                                          --OH per Equivalent of                                                        Epoxy Used in                                                                 Composition                                                                   Equivalents of                                                                             0.1  0.1  0.1  0.1  0.0                                          Sulfanilamide --NH per                                                        Equivalent of Epoxy Used                                                      in Composition                                                                Weight Percent                                                                             0    25.0 34.3 63.7 62.1                                         Diglycidyl Ether of 4,4'                                                      Dihydroxy-alpha-                                                              methylstilbene Used in                                                        Composition                                                                   Weight Percent 4,4'-                                                                       0    0    8.79 16.2 19.7                                         Dihydroxy-alpha-                                                              methylstilbene Used in                                                        Composition                                                                   Casting Appearance                                                                         Trans-                                                                             Trans-                                                                             Trans-                                                                             Trans-                                                                             Trans-                                                    lucent                                                                             lucent                                                                             lucent                                                                             lucent                                                                             lucent                                       Morphology of Cured                                                                        Non- Bire-                                                                              Bire-                                                                              Bire-                                                                              Bire-                                        Composition, Cross-                                                                        Bire-                                                                              fringent                                                                           fringent                                                                           fringent                                                                           fringent                                     polarized Light                                                                            fringent                                                         Microscopy (70X                                                               Maanification)                                                                Fracture Toughness (G.sub.IC),                                                             272  400  729  1197 1953                                         joules/m.sup.2                                                                Methyl Ethyl Ketone                                                                        7.6  1.2  1.0  0.2  0.4                                          Absorption after 8 Hours                                                      Submersion at Room                                                            Temperature, Weight %                                                         Glass Transition                                                                           139  143  137  139  125                                          Temperature, °C.                                                       (Differential Scanning                                                        Calorimetry)                                                                  __________________________________________________________________________     *Not an example of the present invention.                                

TEST PROCEDURES

Fracture Toughness

The method used for measuring fracture toughness or "critical energyrelease rate", (G_(IC)), is an adaption of ASTM E-399 for plasticmaterials from the original usage with metals. This test has widespreadapplication in the measurement of toughness for plastic materials and isdescribed in J. Mater. Sci., Vol. 16, 2657, 1981, which is incorporatedherein by reference in its entirety.

Methyl Ethyl Ketone Absorption

Weighed coupons (1.5 inch×0.5 inch×0.125 inch; 3.81 cm×1.27 cm×0.3175cm) obtained from the castings prepared are submersed in methyl ethylketone. After 8 hours submersion at room temperature, the coupons areremoved from the methyl ethyl ketone, wiped dry, and then reweighed. Themethyl ethyl ketone absorption is then calculated from the weight gainobserved after this exposure.

EXAMPLE 5

Preparation of a Cured Epoxy Resin Composition Containing the DiglycidylEther of 4'-Dihydroxy-alpha-methylstilbene and4,4'-Dihydroxy-alpha-methylstilbene

A. Preparation of B-Staged Resin

The following components are combined and heated to 150° C. in astirred, 2 liter resin kettle:

1. Diglycidyl ether of 4,4'-dihydroxy-alpha-methylstilbene--135.75grams--(EEW =178.08; 0.762 epoxide equiv.),

2. A 3.6 functional phenol/formaldehyde novolac resin--39.64 grams (--OHequiv. wt. =104.0; 0.381 phenolic equiv.).

After heating to 150° C., 34.50 grams of4,4'-dihydroxy-alpha-methylstilbene (--OH equiv. wt. =113.145; 0.305--OH equiv.) is added. After the 4,4'-dihydroxy-alpha-methylstilbene hasdissolved (10 minutes after addition), the temperature of the resin isincreased to 160° C. and 3.28 grams of sulfanilamide (amine hydrogenequiv. wt. =43.0525; 0.076 amine hydrogen equiv.) is added. After thesulfanilamide has dissolved (approximately 10 minutes after addition),the resin is cooled to 140° C. and 1.60 milliliters (0.00185 mole;0.00199 mole of catalyst per epoxide group) of a 40 wt. percent solutionof tetra-n-butylphosphonium fluoroborate (422.5 molecular weight) inmethanol is added and the resultant mixture is stirred for 1 minute. Themethanol is then removed from the B-staged applying a vacuum using abell jar.

B. Curing of B-Staged Resin

After the methanol is removed, as evidenced by no observable outgassing,the B-staged resin prepared in A. above is poured into a 5.5 inch×5.0inch×0.25 inch glass mold preheated to 150° C. The oven temperature isthen reduced to 135° C. and the schedule used to cure the resin is 4hours at 135° C., 1 hour at 150° C., 1 hour at 175° C. and 2 hours at200° C. The casting obtained is cooled to room temperature and removedfrom the mold. From this casting, double-notch four-point bend specimensare prepared for the determination of fracture mechanisms. Thedouble-notch four-point bending technique is described by H.-J. Sue andA. F. Yee in the "Study of fracture mechanisms of multiphase polymersusing the double-notch four-point bending method", Journal of MaterialScience, volume 28 (1993), which is incorporated herein by reference inits entirety. The principle for this technique is as follows: two nearlyidentical cracks are cut using a notching cutter (250 microns inradius), followed by liquid nitrogen chilled razor blade tapping towedge open the sharp cracks into the same edge of a rectangular beam (5inches×0.5 inches×0.25 inches; 12.7 cm×1.27 cm×0.635 cm). This beam isthen loaded in a four-point bending geometry with the cracks positionedon the tensile side. The portion of the beam between the two innerloading points is subjected to a constant bending moment using a Sintech2 screw driven mechanical testing machine. Thus the two cracksexperience nearly identical stresses. As load is applied (crossheadspeed of the testing machine =0.2 inches,5.08 cm, per minute), plasticzones form in front of the crack tips. Since the two cracks cannot beexactly identical, one crack will propagate unstably, leaving behind theother crack with a nearly critically developed process zone at its tip.Since this crack is arrested, the events in the crack tip process arenot obliterated and can be examined. When viewed by scanning electronmicoscopy, the fracture surface produced by the cured resin compositioncontaining the diglycidyl ether of 4,4'-dihydroxy-alpha-methylstilbeneand 4,4'-dihydroxy-alpha-methylstilbene exhibits a rough, tendril-likeappearance indicative of high toughness and ductility. By way ofcontrast, conventional epoxy resins, such as prepared in ComparativeExample A, exhibit a smooth, glassy, featureless surface. Thinsectioning of the crack tip damage zone and microscopy are then appliedto probe the fracture mechanisms which occur at the crack tip and itswake. In examinations of the crack tip damage zone using a JEOL 2000FXATEM transmission electron microscope operating at an acceleratingvoltage of 100 kV, bridging regions of stretched polymer are observedwithin the crack, giving the crack a segmented appearance. Thisobservation indicates that the toughness for this cured compositionresults from a high degree of plastic stretching which has occurredaround the advancing crack tip. An observation made by opticalmicroscopy is that the damage zone surrounding the crack is highlycompact (approximately 30 microns) relative to the damage zone observedin other toughened epoxy resin systems such as, for example, rubbermodified epoxy resin systems (damage zone = approximately 300 microns).

COMPARATIVE EXPERIMENT B

Preparation of a Curable Epoxy Resin Composition Containing theDiglycidyl Ether of 4,4'-Dihydroxy-alpha-methylstilbene and4,4'-Dihydroxy-alpha-methylstilbene Using a Non-Cure Controlling CuringCatalyst

Preparation of B-Staged Resin

34.63 grams of the diglycidyl ether of4,4'-dihydroxy-alpha-methylstilbene (EEW=179.337; 0.193 epoxide equiv.)is placed in a forced air convection oven preheated to 160° C. Afterthis resin has been heated to 160° C., 8.74 grams of4,4'-dihydroxy-alpha-methylstilbene (--OH equiv. wt. =113.145; 0.077--OH equiv.) is added and periodic stirring of the mixture (every 3-4minutes) is begun. After the 4,4'-dihydroxy-alpha-methylstilbene hasdissolved (25 minutes after addition to the resin), 4.99 grams ofsulfanilamide (amine hydrogen equiv. wt. =43.0525; 0.116 amine hydrogenequiv.) is added and periodic stirring is continued. After thesulfanilamide has dissolved (9 minutes after addition to the resin),theresin is cooled to 120° C. After cooling the resin to 120° C. (16minutes after the addition of the sulfanilamide to the resin), 0.22milliliters (0.000412 mole; 0.00199 mole of catalyst per epoxide group)of a 70.9 wt. percent solution of tetra-n-butylphosphoniumacetate.acetic acid complex (378.0 molecular weight) in methanol isadded and the resultant mixture is continuously stirred for 1 minute.The methanol is then removed from the B-staged resin by applying avacuum using a bell jar. After the methanol is removed, the B-stagedresin is cooled to room temperature. Differential scanning calorimetry(DSC) analysis and viscosity data for this curable B-staged epoxy resincomposition are given in Table II.

EXAMPLE 6

Preparation of a Cured Epoxy Resin Composition Containing the DiglycidylEther of 4,4'-Dihydroxy-alpha-methylstilbene and4,4'-Dihydroxy-alpha-methylstilbene

A. Preparation of B-Staged Resin

52.91 grams of the diglycidyl ether of4,4'-dihydroxy-alpha-methylstilbene (EEW=178.137; 0.297 epoxide equiv.)is placed in a forced air convection oven preheated to 160° C. Afterthis resin has been heated to 160° C., 6.72 grams of4,4'-dihydroxy-alpha-methylstilbene (--OH equiv. wt. =113.145; 0.059--OH equiv. ) is added and periodic stirring of the mixture (every 3-4minutes) is begun. After the 4,4'-dihydroxy-alpha-methylstilbene hasdissolved (9 minutes after addition to the resin), 10.23 grams ofsulfanilamide (amine hydrogen equiv. wt. =43.0525; 0.238 amine hydrogenequiv. ) is added and periodic stirring is continued. After thesulfanilamide has dissolved (12 minutes after addition to the resin),0.625 milliliters (0.000722 mole; 0.00199 mole of catalyst per epoxidegroup) of a 40 weight percent solution of tetra-n-butylphosphoniumfluoroborate (422.5 molecular weight) in methanol is added and theresultant mixture is continuously stirred for 1 minute. The methanol isthen removed from the B-staged resin by applying a vacuum using a belljar.

B. Curing of B-Staged Resin

After the methanol is removed, as evidenced by no observable outgassing,the B-staged resin prepared in A. above is poured into a 7.0 inch×7.0inch×0.125 inch (17.78 cm×17.78 cm×0.3175 cm) glass mold preheated to150° C. The schedule used to cure the resin is 4 hours at 150° C., 1hour at 175° C. and 4 hours at 200° C. The casting obtained using thiscure schedule is cooled to room temperature and removed from the moldfor evaluation. The resultant cured product has the properties reportedin Table III.

EXAMPLE 7

Preparation of a Cured Epoxy Resin Composition Containing the DiglycidylEther of 4,4'-Dihydroxy -alpha-methylstilbene and4,4'-Dihydroxy-alpha-methylstilbene

A. Preparation of B-Staged Resin

52.91 grams of the diglycidyl ether of4,4'-dihydroxy-alpha-methylstilbene (EEW =178.137; 0.297 epoxide equiv.)is placed in a forced air convection oven preheated to 160° C. Afterthis resin has been heated to 160° C., 6.72 grams of4,4'-dihydroxy-alpha-methylstilbene (--OH equiv. wt.=113.145; 0.059 --OHequiv.) is added and periodic stirring of the mixture (every 3-4minutes) is begun. After the 4,4'-dihydroxy-alpha-methylstilbene hasdissolved (23 minutes after addition to the resin), 10.23 grams ofsulfanilamide (amine hydrogen equiv. wt.=43.0525; 0.38 amine hydrogenequiv.) is added and periodic stirring is continued. After thesulfanilamide has dissolved (12 minutes after addition to the resin),0.84 milliliters (0.000971 mole; 0.00199 mole of catalyst per epoxidegroup) of a 40 weight percent solution of tetra-n-butylphosphoniumfluoroborate (422.5 molecular weight) in methanol is added and theresultant mixture is continuously stirred for 1 minute. The methanol isthen removed from the B-staged resin by applying a vacuum using a belljar.

B. Curing of B-Staged Resin

B-staged resin prepared in A. above is poured into a 7.5 inch×7.0inch×0.125 inch (19.05 cm×17.78 cm×0.3175 cm) glass mold preheated to160° C. The oven temperature is then reduced to 120° C. and the scheduleused to cure the resin is 4 hours at 120° C., 1 hour at 140° C., 1 hourat 160° C., 1 hour at 180° C. and 4 hours at 200° C. The castingobtained using this cure schedule is cooled to room temperature andremoved from the mold for evaluation. The resultant cured product hasthe properties reported in Table III.

EXAMPLE 8

Preparation of a Cured Epoxy Resin Composition Containing the DiglycidylEther of 4,4'-Dihydroxy-alpha-methylstilbene and4,4'-Dihydroxy-alpha-methylstilbene

A. Preparation of B-Staged Resin

55.61 grams of the diglycidyl ether of4,4'-dihydroxy-alpha-methylstilbene (EEW=178.137; 0.312 epoxide equiv.)is placed in a forced air convection oven preheated to 160° C. Afterthis resin has been heated to 160° C., 14.13 grams of4,4'-dihydroxy-alpha-methylstilbene (--OH equiv. wt.=113.145; 0.125 --OHequiv.) is added and periodic stirring of the mixture (every 3-4minutes) is begun. After the 4,4'-dihydroxy-alpha-methylstilbene hasdissolved (20 minutes after addition to the resin), 8.064 grams ofsulfanilamide (amine hydrogen equiv. wt.=43.0525; 0.187 amine hydrogenequiv.) is added and periodic stirring is continued. After thesulfanilamide has dissolved (9 minutes after addition to the resin),0.650 milliliters (0.000751 mole; 0.00197 mole of catalyst per epoxidegroup) of a 40 weight percent solution of tetra-n-butylphosphoniumfluoroborate (422.5 molecular weight) in methanol is added and theresultant mixture is continuously stirred for 1 minute. The methanol isthen removed from the B-staged resin by applying a vacuum using a belljar.

B. Curing of B-Staged Resin

After the methanol is removed, as evidenced by no observable outgassing,the B-staged resin prepared in A. above is poured into a 7.0 inch×7.0inch×0.125 inch (17.78 cm×17.78 cm×0.3175 cm) glass mold preheated to150° C. The differential scanning calorimetry analysis and viscositydata for this curable composition are given in Table II. The scheduleused to cure the resin is 4 hours at 150° C., 1 hour at 175° C. and 4hours at 200° C. The casting obtained using this cure schedule is cooledto room temperature and removed from the mold for evaluation. Theresultant cured product has the properties reported in Table III.

                  TABLE II                                                        ______________________________________                                                         Comp.                                                        COMPONENTS & RESULTS                                                                           Expt. B*    Ex. 8                                            ______________________________________                                        Equivalents of --OH to                                                                         0.4         0.4                                              Equivalents of Epoxy Used in                                                  Composition                                                                   Equivalents of Sulfanilamide                                                                   0.6         0.6                                              --NH per Equivalent of Epoxy                                                  Used in Composition                                                           Catalyst         tetra-n-butyl                                                                             tetra-n-butyl                                                     phosphonium phosphonium                                                       acetate.acetic                                                                            fluoborate                                                        acid complex                                                 Equivalents of Catalyst per                                                                    0.002       0.002                                            Equivalent of Epoxy Used in                                                   Composition                                                                   Differential Scanning                                                         Calorimetry Analysis.sup.1 :                                                  Onset of Cure Exotherm, °C.                                                             107         183                                              Peak of Cure Exotherm, °C.                                                              168         203                                              Energy of Cure Exotherm,                                                                       202         204                                              joules/gram                                                                   Viscosity Data:                                                               Minimum Viscosity Obtained                                                    on Heating,                                                                   centipoise       1,180 @ 120° C.                                                                      190 @ 172° C.                           Pa · s  1.180 @ 120° C.                                                                    0.190 @ 172° C.                           Viscosity @ 120° C.,                                                   centipoise       1,180       460                                              Pa · s  1.180       0.460                                            Viscosity After 5 Minutes                                                     @ 120° C.,                                                             centipoise       3,040       486                                              Pa · s  3.040       0.486                                            Viscosity After 10 Minutes                                                    @ 120° C.,                                                             centipoise       17,770      561                                              Pa ·  s 17.770      0.561                                            Viscosity After 15 Minutes                                                    @ 120° C.,                                                             centipoise       208,640     647                                              Pa · s  208.640     0.647                                            ______________________________________                                         *Not an example of the present invention                                      .sup.1 Differential scanning caliometry was conducted at 10°           C./minute under a nitrogen atmosphere                                    

EXAMPLE 9

Preparation of a Cured Epoxy Resin Composition Containing the DiglycidylEther of 4,4'-Dihydroxy -alpha-methylstilbene and4,4'-Dihydroxy-alpha-methylstilbene

A. Preparation of B-Staged Resin

55.37 grams of the diglycidyl ether of4,4'-dihydroxy-alpha-methylstilbene (EEW =178.137; 0.311 epoxide equiv.)is placed in a forced air convection oven preheated to 160° C. Afterthis resin has been heated to 160° C., 14.07 grams of4,4'-dihydroxy-alpha-methylstilbene (--OH equiv. wt.=113.145; 0.124 --OHequiv.) is added and periodic stirring of the mixture (every 3-4minutes) is begun. After the 4,4'-dihydroxy-alpha-methylstilbene hasdissolved (25 minutes after addition to the resin), 8.03 grams ofsulfanilamide (amine hydrogen equiv. wt.=43.0525; 0.187 amine hydrogenequiv.) is added and periodic stirring is continued. After thesulfanilamide has dissolved (10 minutes after addition to the resin),0.65 milliliters (0.000751 mole; 0.00198 mole of catalyst per epoxidegroup) of a 40 weight percent solution of tetra-n-butylphosphoniumfluoroborate (422.5 molecular weight) in methanol is added and theresultant mixture is continuously stirred for 1 minute. The methanol isthen removed from the B-staged resin by applying a vacuum using a belljar.

Curing of B-Staged Resin

After the methanol is removed, as evidenced by no observable outgassing,the B-staged resin prepared in A. above is poured into a 7.0 inch×7.0inch×0.125 inch (17.78 cm×17.78 cm×0.3175 cm) glass mold preheated to160° C. The oven temperature is then reduced to 120° C. and the scheduleused to cure the resin is 4 hours at 120° C., 1 hour at 140° C., 1 hourat 160° C., 1 hour at 180° C. and 4 hours at 200° C. The castingobtained using this cure schedule is cooled to room temperature andremoved from the mold for evaluation. The resultant cured product hasthe properties reported in Table III.

COMPARATIVE EXPERIMENT C

Preparation of a Cured Epoxy Resin Composition Containing the DiglycidylEther of 4,4'-Dihydroxy-alpha-methylstilbene and4,4'-Dihydroxy-alpha-methylstilbene Using a Non-Latent Curing Catalyst

The B-staged resin is prepared using the method of ComparativeExperiment B. Curing of the B-staged resin is completed as follows:After the methanol is removed, as evidenced by no observable outgassing,the B-staged resin is poured into a 7.0 inch×7.0 inch×0.125 inch (17.78cm×17.78 cm×0.3175 cm) glass mold preheated to 150° C. The schedule usedto cure the resin is 4 hours at 150° C., 1 hour at 175° C. and 4 hoursat 200° C. The casting obtained using this cure schedule is cooled toroom temperature and removed from the mold for evaluation. The resultantcured product has the properties reported in Table III.

                                      TABLE III                                   __________________________________________________________________________                                    Comp.                                                                         Expt.                                         COMPONENTS AND RESULTS                                                                         Ex. 6                                                                              Ex. 7                                                                              Ex. 8                                                                              C     Ex. 9                                   __________________________________________________________________________    Equivalents of phenolic                                                                        0.2  0.2  0.4  0.4   0.4                                     --OH per Equivalent of                                                        Epoxy Used in Composition                                                     Equivalents of   0.8  0.8  0.6  0.6   0.6                                     Sulfanilamide --NH per                                                        Equivalent of Epoxy Used                                                      in Composition                                                                Initial Curing   150  120  150  150   120                                     Temperature, °C.                                                       Appearance of Casting                                                                          Trans-                                                                             Opaque                                                                             Trans-                                                                             Trans-                                                                              Opaque                                                   lucent    lucent                                                                             lucent                                        Morphology of Cured                                                                            Bire-                                                                              Bire-                                                                              Bire-                                                                              Low   Bire-                                   Composition, Cross-                                                                            fringent;                                                                          fringent;                                                                          fringent;                                                                          level fringent;                               polarized Light Microscopy                                                                     Liquid                                                                             Liquid                                                                             Liquid                                                                             of    Liquid                                  (70X Magnification)                                                                            Crystal                                                                            Crystal                                                                            Crystal                                                                            Bire- Crystal                                                  Textures                                                                           Textures                                                                           Textures                                                                           fringence;                                                                          Textures                                                 Observ-                                                                            & ≦15                                                                       Observ-                                                                            No    & ≦5                                              ed; No                                                                             Micron                                                                             ved; No                                                                            Liquid                                                                              Micron                                                   Disper-                                                                            Domains                                                                            Disper-                                                                            Crystal                                                                             Domains                                                  sed  Observ-                                                                            sed  Textures;                                                                           Observed;                                                Crystals                                                                           ed; No                                                                             Crystals                                                                           Minor No                                                       Observed                                                                           Dispers-                                                                           Observed                                                                           Amount                                                                              Dispersed                                                     ed        of    Crystals                                                      Cryst-    Dispers-                                                                            Observed                                                      als       ed                                                                  Observ-   Cryst-                                                              ed        als                                           Fracture Toughness, (G.sub.IC),                                                                444  942  635  430   915                                     joules/m.sup.2                                                                Flexural Strength,                                                            (ASTM Method D 790),                                                          psi              12,990                                                                             13,635                                                                             11,565                                                                             12,556                                                                              12,055                                  kPa              89,563                                                                             94,010                                                                             79,738                                                                             86,561                                                                              83,116                                  Flexural Modulus (ASTM                                                        Method D 790),                                                                psi              426,000                                                                            417,000                                                                            379,000                                                                            378,000                                                                             386,000                                 kPa              2,937,166                                                                          2,875,114                                                                          2,613,113                                                                          2,606,218                                                                           2,661,376                                                6    14   3    18                                            Glass Transition >237 204  199  201   196                                     Temperature, 2 C.                                                             (Dynamic Mechanical                                                           Analysis)                                                                     __________________________________________________________________________

EXAMPLE 10

Preparation of a Cured Epoxy Resin Composition Containing the DiglycidylEther of 4,4'-Dihydroxy-alpha-methylstilbene and4,4'-Dihydroxy-alpha-methylstilbene

A. Preparation of B-Staged Resin

100.36 grams of the diglycidyl ether of4,4'-dihydroxy-alpha-methylstilbene (EEW =176.6; 0.568 epoxide equiv.)is placed in a forced air convection oven preheated to 160° C. Afterthis resin has been heated to 160° C., 25.72 grams of4,4'-dihydroxy-alpha-methylstilbene (--OH equiv. wt.=113.145; 0.227 --OHequiv.) is added and periodic stirring of the mixture (every 3-4minutes) is begun. After the 4,4'-dihydroxy-alpha-methylstilbene hasdissolved (26 minutes after addition to the resin), 14.68 grams ofsulfanilamide (amine hydrogen equiv. wt.=43.0525; 0.341 amine hydrogenequiv.) is added and periodic stirring is continued. After thesulfanilamide has dissolved (14 minutes after addition to the resin),1.19 milliliters (0.001375 mole; 0.00198 mole of catalyst per epoxidegroup) of a 40 weight percent solution of tetra-n-butylphosphoniumfluoroborate (422.5 molecular weight) in methanol is added and theresultant mixture is continuously stirred for 1 minute. The methanol isthen removed from the B-staged resin by applying a vacuum using a belljar.

Curing of B-Staged Resin

After the methanol is removed, as evidenced by no observable outgassing,the B-staged resin prepared in A. above is poured into a 5.5 inch×5.0inch×0.25 inch (13.97 cm×12.7 cm×0.635 cm) glass mold preheated to 160°C. The oven temperature is then reduced to 120° C. and the schedule usedto cure the resin is 4 hours at 120° C., 1 hour at 140° C., 1 hour at160° C., 1 hour at 180° C. and 4 hours at 200° C. The casting obtainedis cooled to room temperature and removed from the mold. From thiscasting, double-notch four-point bend specimens are prepared for thedetermination of fracture mechanisms. The double-notch four-pointbending technique is described by H.-J. Sue and A. F. Yee in the "Studyof fracture mechanisms of multiphase polymers using the double-notchfour-point bending method", Journal of Material Science, volume 28(1993), which is incorporated herein by reference in its entirety. Theprinciple for this technique is as follows: two nearly identical cracksare cut using a notching cutter (250 microns in radius), followed byliquid nitrogen chilled razor blade tapping to wedge open the sharpcracks into the same edge of a rectangular beam (5 inches×0.5 inch×0.25inch; 12.7 cm×1.27 cm×0.635 cm). This beam is then loaded in afour-point bending geometry with the cracks positioned on the tensileside. The portion of the beam between the two inner loading points issubjected to a constant bending moment using a Sintech 2 screw drivenmechanical testing machine. Thus the two cracks experience nearlyidentical stresses. As load is applied (crosshead speed of the testingmachine=0.2 inch (0.508 cm) per minute), plastic zones form in front ofthe crack tips. Since the two cracks cannot be exactly identical, onecrack will propagate unstably, leaving behind the other crack with anearly critically developed process zone at its tip. Since this crack isarrested, the events in the crack tip process are not obliterated andcan be examined. When viewed by scanning electron micoscopy, thefracture surface produced by the cured resin composition containing thediglycidyl ether of 4,4'-dihydroxy-alpha-methylstilbene and4,4'-dihydroxy-alpha-methylstilbene exhibits a rough, tendril-likeappearance indicative of high toughness and ductility. By way ofcontrast, conventional epoxy resins, such as prepared in ComparativeExample A, exhibit a smooth, glassy, featureless surface. Thinsectioning of the crack tip damage zone and microscopy are then appliedto probe the fracture mechanisms which occur at the crack tip and itswake. In examinations of the crack tip damage zone using a JEOL 2000FXATEM transmission electron microscope operating at an acceleratingvoltage of 100 kV, a birfurcated, highly branched crack containingsegmented and bridged regions of polymer within the crack is observed.Another observation made by transmission electron microscopy is that thespherical liquid crystal domains present in the cured composition aredistorted to elongated liquid crystal domains in the crack wake. Thistype of behavior may be indicative of transformation or orientationaltoughening.

EXAMPLE 11

Preparation of a Glass Laminate Containing the Diglycidyl Ether of4,4'-Dihydroxy-alpha-methylstilbene

A. Preparation of B-Staged Resin

The following components are combined and heated to 150° C. in astirred, 2 liter resin kettle:

1. The diglycidyl ether of 4,4'-dihydroxy-alpha-methylstilbene--160.23grams--(EEW=179.337; 0.893 epoxide equiv. ) ,

2. Tetrabromobisphenol A--49.06 grams (--OH equiv. wt.=272.0; 0. 180phenolic equiv. )

After heating to 150° C., 30.70 grams of sulfanilamide (amine hydrogenequiv. wt.=43.0525; 0.713 amine hydrogen equiv.) is added. After thesulfanilamide has dissolved (approximately 8 minutes after addition),1.70 milliliters (0.001964 mole; 0.00198 mole of catalyst per epoxidegroup) of a 40 weight percent solution of tetra-n-butylphosphoniumfluoroborate (422.5 molecular weight) in methanol is added and theresultant mixture is stirred for 1 minute. The methanol is then removedfrom the B-staged resin by applying a vacuum to the resin kettle.

B. Preparation of Cured Glass Laminate Using B-Staged Resin

After the methanol is removed, as evidenced by no observable outgassing,the B-staged resin prepared in A. above is poured onto a mold platewhich is at room temperature (approximately 23° C.). 270 grams of a 9ply preform prepared from glass fabric is then applied to the top of theresin. The glass fabric used is obtained from BGF Industries, Inc. andhas a designation for style and finish of 7628 and I621, respectively. Asealed mold is then constructed around the resin and preform by boltingdown to the mold plate a steel picture frame (15.25 inch ID×15.25 inchID×0.25 inch (38.735 cm×38.735 cm×0.635 cm) deep) covered with a 0.004inch thick film of polyimide (UPILEX™ marketed by ICI Films). This moldis then placed in a mechanical press where full vacuum is applied to themold using a vacuum pump. The press is then heated to 120° C. over a18.5 minute period. After holding the temperature at 120° C. for 11.7minutes, 200 pounds per square inch pressure is applied to the moldusing the mechanical press. After applying this pressure, the cureschedule used for the laminate is 5 hours at 120° C., 1 hour at 140° C.,1 hour at 160° C., 1 hour at 180° C. and 4 hours at 200° C. After 4hours at 200° C., the mold is cooled to room temperature and thelaminate (15.25 inch×15.25 inch×0.064 inch) is removed. The propertiesfor the laminate are given below:

1. Glass transition temperature by differential scanningcalorimetry=180° C.;

2. Burn time in UL-94 test (5 specimens/10 burns) =55.7 seconds;

3. Methylene chloride absorption after 30 minutes submersion at roomtemperature=0.04 weight percent;

4. No blistering observed for ten 2 inch×3 inch (5.08 cm×7.62 cm)samples exposed to autoclave conditions of 250° F. and 15 psi (103.421kPa) for 2 hours followed by a 20 second solder dip at 550° F.;

5. Room Temperature Dielectric Properties=see Table IV.

TABLE IV

Room Temperature Dielectric Properties for Laminate Prepaared in Example11

    ______________________________________                                                        Dielectric                                                                              Dissipation                                         Freqency, KHz   Constant  Factor                                              ______________________________________                                        1.00            5.243     0.01125                                             2.00            5.215     0.01269                                             5.00            5.173     0.01474                                             10.00           5.137     0.01612                                             20.00           5.098     0.01721                                             50.00           5.044     0.01808                                             100.00          5.002     0.01848                                             ______________________________________                                    

What is claimed is:
 1. A laminate comprising one or more plies of asubstrate material which has been impregnated with a product resultingfrom B-staging (partially curing ) a curable composition comprising;(A)at least one epoxy resin having an average of more than one vicinalepoxide group per molecule; (B) at least one curing agent for said epoxyresin in an amount which provides from about 0.8 to about 1.5equivalents of curing agent per epoxide group; and (C) about 0.00005 toabout 0.1 mole per epoxide equivalent of a cure controlling catalystrepresented by any of the following formulas: ##STR8## wherein each L isindependently a hydrocarbyl group or inertly substituted hydrocarbylgroup having from 1 to about 18 carbon atoms, which group also cancontain one or more oxygen, sulfur or nitrogen atoms or two of such Lgroups can combine to form a heterocyclic ring containing one or moreatoms other than carbon atoms; each L¹ is independently hydrogen or L; Zis nitrogen, phosphorus, sulfur or arsenic; W is a weak nucleophilicanion selected from the group consisting of BF₄ ⁻, BCl₄ ⁻, NO₃ ⁻, F⁻,Cl--CH₂ --CH₂ --CO₂ ⁻, HO--CH₂ --CH₂ --CO₂ ⁻ SbF₅ ⁻, SbCl₆ ⁻, AsF₄ ⁻,AsCl₄ ⁻, FP(O)₂ (OH)⁻,(F)₂ P(O)₂ ⁻, F₃ B(OH)--, F₂ B(OH)₂ -- and ClP(O)₂(OH)⁻ and z has a value of zero or 1 depending on the valence ofZ;wherein at least one epoxy resin of component (A) is an epoxy resinwhich contains at least one mesogenic moiety represented by any one ormore of the following formulas: ##STR9## wherein: each R isindependently hydrogen or a monovalent hydrocarbyl or hydrocarbyloxygroup having from one to about carbon atoms, a halogen atom, a nitrogroup, a nitrile group or a --CO--R² group; R² is hydrogen or amonovalent hydrocarbyl group having from one to about 10; n has a valueof zero or one; each A is independently a direct single bond, a divalenthydrocarbyl group having from one to about carbon atoms, --O--, --CO--,--SO--, --SO₂ --, --S--, --S--S--, --CR¹ ═CR¹ --, --C.tbd.C--, --N═N--,--CR¹ ═N--, --N═CR¹ --, --O--CO--, --CO--O--, --S--CO--, --CO--S--,--NR¹ --CO--, --CO--NR¹ --, --CR¹ ═N--N═CR¹ --, --CO--CR¹ ═CR¹ --, --CR¹═CR¹ --CO--, --CR¹ ═N--O--OC--, --CO--O--N═CR¹ --, --CO--NR¹ --NR¹--OC--, --CR¹ ═CR¹ --O--OC--, --CO--O--CR¹ ═CR¹ --, --O--CO--CR¹ ═CR¹--, --CR¹ ═CR¹ --CO--O--, --(CHR¹)_(n') --O--CO--CR¹ ═CR¹ --, --CR¹ ═CR¹--CO--O--(CHR¹)_(n') --, --(CHR¹)_(n') --CO--O--CR¹ ═CR¹ --, --CR¹ ═CR¹--O--CO--(CHR¹)_(n') --, --CH₂ --CH₂ --CO--O--, --O--OC--CH₂ --CH₂ --,--C.tbd.C--C.tbd.C--, --CR¹ ═CR¹ --CR¹ ═CR¹ --, --CR¹ ═CR¹ --C.tbd.C--,-- C.tbd.C--CR¹ ═CR¹ --, --CR¹ ═CR¹ --CH₂ --O--OC--, --CO--O--CH₂ --CR¹═CR¹ --, --O--CO--C.tbd.C--CO--O--, --O--CO--CR¹ ═CR¹ --CO--O--,--O--CO--CH₂ --CH₂ --CO--O--, --S--CO--CR¹ ═CR¹ --CO--S--, --CO--CH₂--NH--CO--, --CO--NH--CH₂ --CO--, --NH--C(--CH₃)═CH--CO--,--CO--CH═C(--CH₃)--NH--, --CR¹ ═C(--Cl)--, --C(--Cl)═CR¹ --, --CR¹═C(--CN)--, --C(--CN)═CR¹ --, --N═C(--CN)--, --C(--CN)═N--, --CR¹═C(--CN)--CO--O--, --O--CO--C(--CN)═CR¹ --, ##STR10## each A" is adivalent hydrocarbyl group having from one to about 6 carbon atoms; eachA¹ is independently a --CO--, --O--CO--, --CO--O--, --CO--S--,--S--CO--, --CO--NR¹ -- or --NR¹ --CO--; each R¹ is independentlyhydrogen or a monovalent hydrocarbyl group having from one to about 6carbon atoms; each R⁴ is independently hydrogen or a monovalenthydrocarbyl group having from one to about 3 carbon atoms; n' has avalue of one or two; p has a value from zero to about 30; and p¹ has avalue of from one to about 30, which, optionally, has been subjected toeither (a) the application of an electric field, (b) the application ofa magnetic field, (c) drawing or shear forces, or (d) any combinationthereof.
 2. The laminate of claim 1 wherein the substrate material is afibrous glass material or a fibrous graphite material.